Use of Hexose Oxidases to Create Hydrogen Peroxide in Aqueous Well Treatment Fluids

ABSTRACT

A hydrocarbon-bearing subterranean formation may be treated with an aqueous well treatment fluid which contains a hexose oxidase, such as glucose oxidase, mannose oxidase or galactose oxidase. The aqueous well treatment fluid further may contain a viscosifying polymer and an aldohexose. The aldohexose reacts in-situ with the hexose oxidase and molecular oxygen to produce hydrogen peroxide. The hydrogen peroxide may then act as a breaker.

FIELD OF THE INVENTION

Hexose oxidases are used for the in-situ creation of hydrogen peroxide,as breaker, for well treatment fluids. The breaker is produced in thepresence of an aldohexose, such as glucose, galactose or mannose. Thealdohexose is either a component of the well treatment fluid or isgenerated in-situ.

BACKGROUND OF THE INVENTION

Hydraulic fracturing is used to create subterranean fractures thatextend from the borehole into the rock in order to increase the rate atwhich fluids can be produced from the formation. Generally, a fracturingfluid is pumped into the well at high pressure. Once natural reservoirpressures are exceeded, the fracturing fluid initiates a fracture in theformation which continues to grow during pumping. The treatment designgenerally requires the fluid to reach maximum viscosity as it enters thefracture.

The fracturing fluid typically contains a proppant which is placedwithin the produced fracture. The proppant remains in the producedfracture to prevent the complete closure of the fracture and to form aconductive channel extending from the wellbore into the treatedformation.

Most fracturing fluids contain a viscosifying agent in order to increasethe capability of proppant transport into the fracture. Suitableviscosifying agents include synthetic polymers, like polyvinyl alcohols,polyacrylates, polypyrrolidones and polyacrylamides, andpolysaccharides, like guar gum (galactomannans) and guar gumderivatives. Exemplary guar or guar gum derivatives includehydroxypropyl guar (HPG), carboxymethyl guar (CMG) andcarboxymethylhydroxypropyl guar (CMHPG) as well as high molecular weightnon-derivatized guar.

Once the high viscosity fracturing fluid has carried the proppant intothe formation, breakers are used to reduce the fluid's viscosity. Inaddition to facilitating settling of the proppant in the fracture, thebreaker also facilitates fluid flowback to the well. Breakers work byreducing the molecular weight of the viscosifying agent. The fracturethen becomes a high permeability conduit for fluids and gas to beproduced back to the well.

Common breakers for use in fracturing fluids include chemical oxidizers,such as hydrogen peroxide and persulfates. Chemical oxidizers produce aradical which then degrades the viscosifying agent. This reaction islimited by the fact that oxidizers work in a stoichiometric fashion suchthat the oxidizer is consumed when one molecule of oxidizer breaks onechemical bond of the viscosifying agent. Further, at low temperatures,such as below 120° F., chemical oxidizers are generally too slow to beeffective and other catalysts are needed to speed the rate of reaction.At higher temperatures, chemical oxidizers function very rapidly andoften must be encapsulated in order to slow the rate of reaction.Alternatives have been sought for maximizing the efficiency of chemicaloxidizers in the well treatment fluid at in-situ conditions.

More recent interest in hydraulic fracturing has focused on slickwaterfracturing which is often used in the stimulation of tight gasreservoirs. In slickwater fracturing, a well is stimulated by pumpingwater at high rates into the wellbore, thereby creating a fracture inthe productive formation. Slickwater fluids are basically fresh water orbrine having sufficient friction reducing agent(s) to minimize tubularfriction pressures. Generally, such fluids have viscosities onlyslightly higher than unadulterated fresh water or brine. Such fluids aremuch cheaper than conventional fracturing fluids which contain aviscosifying agent. In addition, the characteristic low viscosity ofsuch fluids facilitates reduced fracture height growth in the reservoirduring stimulation.

When aqueous fluids (like slickwater fracturing fluids) not containing aviscosifying polymer are used in stimulation, the pressure during thepumping stage is normally lower than that required in fracturingtreatments using viscosifying polymers. The frictional drag of the fracfluid is lowered by the presence of the friction reduction agent(s) inthe slickwater fluid. While slickwater fluids introduce less damage intothe formation in light of the absence of viscosifying polymers, thefriction reduction agent, if left in the formation, can cause formationdamage. Effective means of degrading friction reduction agents inslickwater fracturing fluids is desired in order to minimize damage tothe treated formation.

SUMMARY OF THE INVENTION

A hydrocarbon-bearing subterranean formation may be treated with anaqueous well treatment fluid containing a hexose oxidase. Hydrogenperoxide is generated in-situ by reaction of an aldohexose and oxygen inthe presence of the hexose oxidase. The hydrogen peroxide may act aschemical breaker in the hydrolysis of a viscosifying polymer present inthe well treatment fluid. Alternatively, the hydrogen peroxide mayfunction to degrade a friction reduction agent in a well treatmentfluid. Further, the hydrogen peroxide may function to degrade apolymeric component of a filter cake.

The aldohexose may be a component in the aqueous well treatment fluid.Alternatively, the aldohexose may be generated in-situ.

The aldohexose seeds the reaction for the generation of a small amountof hydrogen peroxide. The hydrogen peroxide produced from the seedreaction breaks at least a portion of the viscosifying polymer, frictionreduction agent or the polymeric component of the filter cake which thenreacts with oxygen, in the presence of the hexose oxidase, to creategreater quantities of hydrogen peroxide. Thus, as the polysaccharideviscosifying agent or polysaccharide-based filter cake degrades, moreand more breaker is produced. This then serves to effectuate thecomplete degradation of the polysaccharide viscosifying agent orpolysaccharide-based filter cake. As such, the polysaccharideviscosifying agent or polysaccharide-based filter cake becomes thesource of the breaker.

As an example, hydrogen peroxide produced from the seed reaction ofaldohexose may break a small portion of a polysaccharide (functioning asviscosifying polymer) in a well treatment fluid into monosaccharideunits. The monosaccharide units then react with oxygen, in the presenceof the hexose oxidase, to create greater quantities of hydrogenperoxide. Degradation of the polysaccharide produces greater quantitiesof breaker which effectuates the complete degradation of thepolysaccharide.

Exemplary of the invention is an aqueous well treatment fluid containingguar, beta D-glucose and glucose oxidase, a flavin-dependent enzyme.Reaction of the glucose with oxygen in the presence of the enzymeproduces hydrogen peroxide and D-glucono-1,5-lactone. Otherbeta-D-monosaccharides, such as galactose and mannose, may also beconverted to lactones by glucose oxidase. As hydrogen peroxide isproduced, it attacks the guar and degrades guar to produce smallermolecular weight fragments including the monosaccharides galactose andmannose. The enzyme can then use these liberated monosaccharides toproduce more hydrogen peroxide which further degrades the guar polymer.

In addition to the embodiment wherein the well treatment fluid is afracturing fluid containing a viscosifying agent, the well treatmentfluid may further be a fracturing fluid containing a polymeric frictionreducer for use in slickwater fracturing. When used as a slickwaterfracturing fluid, the hydrogen peroxide breaks the polymeric frictionreducer. In the manner described above, the hydrogen peroxide isgenerated in situ by reaction of an aldohexose and oxygen in thepresence of an aldohexose.

In addition, the well treatment fluid may be used to clean up a fluidloss pill, typically used during completion of the well. In such aninstance, the well treatment fluid aids in the removal of the filtercake formed by the fluid loss pill. In addition, the well treatmentfluid may be used to remove the filter cake from drilling fluid ordrill-in fluid formed during drilling.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more fully understand the drawings referred to in thedetailed description of the present invention, a brief description ofeach drawing is presented, in which:

FIG. 1 demonstrates the reduction in viscosity of an aqueous fluidcontaining a crosslinked polysaccharide by the action of glucose oxidasewhen seeded with a hexoaldose.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The method disclosed herein consists of treating a hydrocarbon-bearingsubterranean formation penetrated by a wellbore with an aqueous welltreatment fluid which contains a hexose oxidase. The hexose oxidase inthe aqueous well treatment fluid of the invention is preferably glucoseoxidase, mannose oxidase or galactose oxidase. Typically, the amount ofhexose oxidase in the aqueous well treatment fluid is typically betweenfrom about 1.0×10⁻³ to about 1.0 percent by volume.

The aqueous well treatment fluid may further contain a viscosifyingagent. The viscosifying agent serves to increase the viscosity of theaqueous well treatment fluid and is hydrolyzed by the enzymaticallyproduced hydrogen peroxide. When present, the amount of viscosifyingagent in the aqueous well treatment fluid is between from about 0.10% to5.0% by weight of the aqueous fluid. The most preferred range for thepresent invention is about 0.20% to 0.80% by weight.

Preferred viscosifying agents include polysaccharides which may behydrolyzed by the enzymatically produced hydrogen peroxide to formmonosaccharide units and other low molecular weight fragments. Suitablepolysaccharides may be ionic as well as nonionic. Preferred arecellulose, starch, and galactomannan gums, such as non-derivatized andderivatized guar. The polysaccharide may be a microbial polysaccharidesuch as xanthan, succinoglycan and scleroglucan.

Suitable cellulose and cellulose derivatives include alkylcellulose,hydroxyalkyl cellulose or alkylhydroxyalkyl cellulose, carboxyalkylcellulose derivatives such as methyl cellulose, hydroxyethyl cellulose,hydroxypropyl cellulose, hydroxybutyl cellulose, hydroxyethylmethylcellulose, hydroxypropylmethyl cellulose, hydroxylbutylmethyl cellulose,methylhydroxyethyl cellulose, methylhydroxypropyl cellulose,ethylhydroxyethyl cellulose, carboxyethylcellulose,carboxymethylcellulose and carboxymethylhydroxyethyl cellulose.

Specific galactomannan gums and derivatized galactomannan gums includeguar gum, hydroxypropyl guar, carboxymethyl guar, hydroxyethyl guar,hydroxypropyl guar, carboxymethylhydroxyethyl guar,carboxymethylhydroxypropyl guar and known derivatives of these gums.

Particularly preferred are “GW4” (guar), “GW21” (HEC), “GW22” (xanthangum), “GW24L” (HEC slurry), “GW45” (CMG), “GW27” (guar), “GW28” (CMHEC),“GW32” (HPG), and “GW38” (CMHPG), all available from BJ Services CompanyLLC. In addition, slurried counterparts of these polymers are availablefrom BJ Services Company LLC as “XLFC1” (guar), “XLFC1B” (guar), “XLFC2”(HPG), “XLFC2B” (HPG), “XLFC3” (CMPHG) “XLFC3B” (CMHPG), “VSP1” (CMG),and “VSP2” (CMG), respectively.

The viscosifying agent may further be a synthetic polymer such as apolyvinyl alcohol, polyacrylate, polypyrrolidone or polyacrylamide or amixture thereof. In addition, the viscosifying polymer may be a block orrandom copolymer containing units selected from vinyl alcohol,acrylates, including the (meth)acrylates, pyrrolidone,2-acrylamido-2-methylpropane sulfonate and acrylamide including the(meth)acrylamides.

The pH of the well treatment fluid introduced into the wellbore istypically between from about 5.5 to about 10.5 and more typically isbetween from about 8.5 to about 10.5.

When the well treatment fluid introduced contains a viscosifyingpolymer, the fluid further typically contains a crosslinking agent. Anycrosslinking agent capable of hydrogen bonding with the viscosifyingpolymer may be employed.

Suitable crosslinking agents include a borate ion releasing compound, anorganometallic or organic complexed metal ion comprising at least onetransition metal or alkaline earth metal ion as well as mixturesthereof. When present, the amount of crosslinking agent employed in thecomposition is typically between from about 0.001 percent to about 2percent, preferably from about 0.005 percent to about 1.5 percent, and,most preferably, from about 0.01 percent to about 1.0 percent.

Borate ion releasing compounds which can be employed include, forexample, any boron compound which will supply borate ions in the welltreatment fluid, for example, boric acid, alkali metal borates such assodium diborate, potassium tetraborate, sodium tetraborate (borax),pentaborates and the like and alkaline and zinc metal borates. Suchborate ion releasing compounds are disclosed in U.S. Pat. No. 3,058,909and U.S. Pat. No. 3,974,077 herein incorporated by reference. Inaddition, such borate ion releasing compounds include boric oxide (suchas selected from H₃BO₃ and B₂O₃) and polymeric borate compounds. Suchborate-releasers typically require a basic pH (e.g., 7.0 to 12) forcrosslinking to occur. Suitable pH adjustment agents, such as soda ash,potassium hydroxide, sodium hydroxide and alkaline and alkali carbonatesand bicarbonates, may be used to maintained the desired pH.

Further preferred crosslinking agents are organometallic and organiccomplexed metal compounds, which can supply zirconium IV ions such as,for example, zirconium lactate, zirconium lactate triethanolamine,zirconium carbonate, zirconium acetylacetonate and zirconiumdiisopropylamine lactate; as well as compounds that can supply titaniumIV ions such as, for example, titanium ammonium lactate, titaniumtriethanolamine, and titanium acetylacetonate. Zr (IV) and Ti (IV) mayfurther be added directly as ions or oxy ions into the composition.

The aqueous well treatment fluid is used principally to enhance theproductivity of the formation. In a preferred embodiment, the welltreatment fluid is used as a stimulation fluid, such as one used inhydraulic fracturing. The heightened viscosity of the fluid enables thetransport of a proppant into the created fractures. Such proppants serveto prop open the created fractures such that the fracture provideslarger flow channels through which an increased quantity of ahydrocarbon may flow. Productive capability of the well is thereforeincreased.

In addition to the hexose oxidase, the aqueous well treatment fluidsdescribed herein may further contain one or more aldohexoses. Thealdohexose in the well treatment fluid reacts in-situ with the hexoseoxidase and molecular oxygen (within the wellbore) to produce hydrogenperoxide and a lactone. When present, the amount of aldohexose in theaqueous well treatment fluid introduced into the wellbore is thatsufficient to produce, in the presence of the hexose oxidase, a smallamount of hydrogen peroxide. Typically, the amount of aldohexose in theaqueous well treatment fluid is no greater than 0.001 volume percent.The produced hydrogen peroxide may then be used to break down theviscosifying polymer (for example polysaccharide into monosaccharideunits), friction reduction agent or polymeric component of a filter cakewhich in turn then produces additional hydrogen peroxide. In the case ofbreaking synthetic polymeric friction reducers, the amount of aldohexosein the aqueous well treatment fluid is that sufficient to produce thedesired amount of hydrogen peroxide.

When present in the well treatment fluid, the aldohexose functions as amonosaccharide “seed” to commence generation of a small amount ofhydrogen peroxide in-situ by it reaction with oxygen, in the presence ofthe hexose oxidase. Suitable aldohexoses include allose, altrose,glucose, mannose, gulose, idose, galactose and talose.

An exemplary catalytic pathway for glucose oxidase (as hexose oxidase)in the production of hydrogen peroxide in the presence of apolysaccharide is set forth below in Schematic (I) wherein themonosaccharides are represented by the open hexagons, the lactone isrepresented by the cross-hatched hexagon, and the produced carboxylicacid is represented by the filled hexagon:

As illustrated, hydrogen peroxide produced from the seed reaction breaksa small portion of the polysaccharide (viscosifying polymer) intomonosaccharide units. Such monosaccharide units then react with thehexose oxidase and oxygen to create greater quantities of hydrogenperoxide to defragment the polysaccharide. As such, the aldohexose inthe aqueous well treatment fluid when introduced into the wellboreserves as a seed to generate a small amount of hydrogen peroxide; muchlarger amounts of hydrogen peroxide being produced in-situ asdegradation of the polysaccharide continues in the formation.

Typically, the molar ratio of aldohexose to hexose oxidase in theaqueous well treatment fluid introduced into the wellbore to conduct theseed reaction is between from about 1:10 to about 10:1 and the molarratio between the aldohexose, oxygen and hexose oxidase is preferably1:1:1.

Instead of including the aldohexose in the aqueous well treatment fluid,the aldohexose may be generated in-situ. For instance, where the aqueouswell treatment fluid introduced into the wellbore contains apolysaccharide as viscosifying agent, the fluid may further contain asmall amount of a conventional enzyme breaker or chemical breaker, likeperoxide. Such a breaker could defragment a small amount of polymericviscosifying agent into monosaccharide units including aldohexose units.Such in-situ generated aldohexoses may then react with the hexoseoxidase and molecular oxygen to produce hydrogen peroxide, such as inaccordance with Schematic (I) above.

The generation of hydrogen peroxide in accordance with the method of theinvention is believed to proceed by Schematic (II), wherein thealdohexose if glucose:

As shown, in the presence of glucose oxidase, GO_(x), and oxygen (withinthe wellbore and/or formation), glucose is oxidized to its correspondinglactone which hydrolyzes to the corresponding carboxylic acid, acarboxylated derivative of the aldohexose. The reduced form of theglucose oxidase further reacts with oxygen to restore the glucoseoxidase to its initial (oxidized) state and produce hydrogen peroxide.The hydrogen peroxide then degrades the viscosifying polymer, frictionreduction agent or polymeric component of a filter cake into smallerbuilding or molecular units which may then, in turn, react with thehexose oxidase to produce additional hydrogen peroxide by the procedureset forth above.

The viscosity of the well treatment fluid is thereby gradually decreasedby the hydrogen peroxide produced in-situ in the formation from thereaction of the glucose oxidase and aldohexose. The pH is lowered as thecarboxylic acid is generated. In, for example, a well treatment fluidcontaining a viscosifying polymer, the lowering of the pH diminishes theefficacy of the crosslinking agent to hydrogen bonding to thepolysaccharide. The lowering of the pH decreases the viscosity of thewell treatment fluid.

When used as a fracturing fluid, any proppant known in the art may beused in the well treatment fluid. Suitable proppants include quartz sandgrains, glass and ceramic beads, walnut shell fragments, aluminumpellets and nylon pellets.

Other suitable proppants include ultra lightweight proppants having anapparent specific gravity less than or equal to 2.45, preferably lessthan or equal to 1.75, most preferably less than or equal to 1.25.Suitable ULW particulates include those set forth in U.S. PatentPublication No. 20050028979, published on Feb. 10, 2005, hereinincorporated by reference. Included therein are naturally occurringmaterials which may be strengthened or hardened by use of modifyingagents to increase the ability of the naturally occurring material toresist deformation. Specific examples of ULW particulates include, butare not limited to, ground or crushed shells of nuts such as walnut,coconut, pecan, almond, ivory nut, brazil nut, etc.; ground or crushedseed shells (including fruit pits) of seeds of fruits such as plum,olive, peach, cherry, apricot, etc.; ground or crushed seed shells ofother plants such as maize (e.g., corn cobs or corn kernels), etc.;processed wood materials such as those derived from woods such as oak,hickory, walnut, poplar, mahogany, etc., including such woods that havebeen processed by grinding, chipping, or other form of particalization,processing, etc. Further suitable particulates include porous ceramicsor organic polymeric particulates. The porous particulate material maybe treated with a non-porous penetrating material, coating layer orglazing layer. For instance, the porous particulate material may be atreated particulate material, as defined in U.S. Pat. No. 7,426,961,herein incorporated by reference, wherein (a) the ASG of the treatedporous material is less than the ASG of the porous particulate material;(b) the permeability of the treated material is less than thepermeability of the porous particulate material; or (c) the porosity ofthe treated material is less than the porosity of the porous particulatematerial. Further, the ultra lightweight particulate may be a welltreating aggregate composed of an organic lightweight material and aweight modifying agent. The ASG of the organic lightweight material iseither greater than or less than the ASG of the well treating aggregatedepending on if the weight modifying agent is a weighting agent orweight reducing agent, respectively. Where the weight modifying agent isa weighting agent, the ASG of the well treating aggregate is at leastone and a half times the ASG of the organic lightweight material, theASG of the well treating aggregate preferably being at least about 1.0,preferably at least about 1.25. Such ULW proppants are disclosed in U.S.Patent Publication No 2008/0087429 A1, herein incorporated by reference.Further, the ULW proppant may be a polyamide, such as those disclosed inUS-2007-0209795 A1, herein incorporated by reference. Further, the ULWproppant may be metallic spheres, such as those disclosed in U.S. PatentPublication No. 2008/0179057 A1 as well as those deformable particulatesset forth in U.S. Pat. No. 7,322,411, both of which are hereinincorporated by reference. Still preferred are synthetic polymers, suchas polystyrene beads crosslinked with divinylbenzene. Such beads includethose described in U.S. Pat. No. 7,494,711, herein incorporated byreference.

The well treatment fluid described herein can also contain otherconventional additives common to the well service industry such assurfactants, corrosion inhibitors, crosslinking delaying agents and thelike.

In addition to functioning as a stimulation fluid, the aqueous welltreatment fluids described herein may also be used as a well treatmentfluid to clean up a fluid loss pill typically used during completionoperations. In this case, the well treatment fluid aids in the removalof the filter cake formed by the fluid loss pill. The filter cake, insome instance, may become embedded in the formation. The treatment fluidfor such purposes does not contain a viscosifying polymer, such as apolysaccharide. The treatment fluid contains hexose oxidase which reactswith an aldohexose (either in the treatment fluid or generated in-situ)to produce hydrogen peroxide. The hydrogen peroxide is then used tobreak down the polymeric component, such as a polysaccharide, in thefilter cake in the manner described above. The well treatment fluidtherefore assists in the removal of the filter cake defragmenting thepolymeric component present in the filter cake.

Similarly, the aqueous well treatment fluids described herein may alsobe used as a well treatment fluid to remove the filter cake fromdrilling fluid or drill-in fluid formed during drilling operations. Inthis case, the well treatment fluid aids in the removal of the filtercake formed by the drilling fluid or drill-in fluid being depositeddirectly against the formation. The filter cake, in some instance, maybecome embedded in the formation. Removal of the filter cake iseffectuated by breaking down the polymeric component of the filter cakein the manner described above. In particular, the hexose oxidase, inconjunction with the hexoaldose and oxygen, generates hydrogen peroxide.The peroxide, in turn, defragments the polymeric component and breaksthe filter cake.

In another preferred embodiment, the well treatment fluid describedherein is a fracturing fluid for slickwater fracturing. The aqueous welltreatment fluid for slickwater fracturing typically does not contain aviscosifying agent such as a viscosifying polymer. Instead, the welltreatment fluid contains a polymeric friction reducing agent. Thehydrogen peroxide generated in-situ from the reaction of the aldohexoseand oxygen, in the presence of the hexose oxidase, reduces the molecularweight of the friction reducing agent. The defragmented components ofthe friction reducing agent may then be removed from the wellbore andformation damage from the friction reducing agent is thereby minimized.Typically, the friction reducing agent in such applications is apolyacrylamide and polyacrylates. The amount of friction reducing agentsin such well treatment fluids is generally from about 1 to about 8pounds per thousand gallons of water. Such slickwater fracturing methodsare particularly desirous when stimulating shale formations and tightgas sands, as well as limestone.

The following examples are illustrative of some of the embodiments ofthe present invention. Other embodiments within the scope of the claimsherein will be apparent to one skilled in the art from consideration ofthe description set forth herein. It is intended that the specification,together with the examples, be considered exemplary only, with the scopeand spirit of the invention being indicated by the claims which follow.

EXAMPLES Example 1

A 100 mL aqueous fluid was prepared containing 25 ppt of anon-derivatized guar having an intrinsic viscosity of approximately 16.1dL/g (commercially available as GW3 from BJ Services Company LLC), 1.5gpt of buffer (commercially available as BF-7L from BJ Services CompanyLLC), 1.5 gpt of a borate crosslinking agent (commercially available asXLW-32 from BJ Services Company LLC) and about 25 ug/mL of glucoseoxidase, GO_(x). Dextrose was then added at a concentration ofapproximately 3 μM. The resulting fluid was then transferred to aChandler 5500 viscometer having an R1B1 bob and cup assembly. Theviscosity was then measured at 300 rpm (511 sec⁻¹) at 140° F. FIG. 1demonstrates the reduction in viscosity of the crosslinked guar polymerby the action of glucose oxidase. As shown in FIG. 1, glucose oxidasereduces the viscosity of the 25 ppt crosslinked guar polymer when seededwith the 3 mM dextrose. Liberated mannose and galactose monosaccharidesare used by the enzyme to produce hydrogen peroxide and further degradethe crosslinked guar polymer. In the absence of dextrose, FIG. 1 showsthat glucose oxidase does not initiate the reaction and the crosslinkedguar polymer is not broken. FIG. 1 also demonstrates that there is nosignificant rebounding of the viscosity of the broken guar polymer ascompared to the control once the samples are cooled to room temperature.

Example 2

Approximately 5.5 mM of mannose, galactose and glucose were dissolved inthree separate vessels containing distilled water and about 25 ug/mL ofglucose oxidase. The concentration of hydrogen peroxide was thenmeasured by test strips after 5 minutes and 1 hour and the pH of thefluid after one hour was also determined. The results are set forth inTable I below:

TABLE I Sugar [H₂O₂]^(A), mg/L [H₂O₂]^(B), mg/L pH^(B) Mannose 3 10 4.5Galactose 0 3 5.7 Glucose 10 30 3.7 ^(A)5 minute reaction time. ^(B)1hour reaction time.

As shown in Table I, mannose and galactose as well as glucose aresuitable substrates for glucose oxidase. Based on the concentration ofhydrogen peroxide with respect to time, the enzyme's substratespecificity is glucose>mannose>galactose. This is also reflected in thepH of the samples after the 5 minute reaction time. Referring toSequence II above, the production of a carboxylic acid from the oxidizedlactone provides the recorded drop in the pH of the fluid. The pH ofeach of the samples is consistent with the utilization of the substratei.e. the more the reaction progresses, the lower the pH. Additionally,the drop in pH reduces the efficacy of the crosslinking reaction leadingto a further reduction in the viscosity of the fluid.

From the foregoing, it will be observed that numerous variations andmodifications may be effected without departing from the true spirit andscope of the novel concepts of the invention.

1. A method of treating a subterranean formation penetrated by awellbore which comprises: (a) introducing into the wellbore an aqueouswell treatment fluid comprising a viscosifying agent and/or a frictionreducer and a hexose oxidase and increasing the viscosity of the welltreatment fluid in-situ; (b) producing hydrogen peroxide in-situ byreacting an aldohexose and oxygen, in the presence of the hexoseoxidase, (c) reducing the viscosity of the well treatment fluid byreacting the hydrogen peroxide with the viscosifying agent and/orfriction reducer.
 2. The method of claim 1, wherein the aldohexose ofclaim (b) is generated in-situ.
 3. The method of claim 2, wherein thealdohexose is produced in-situ by reacting the polysaccharide and/orfriction reducer with an enzyme or hydrogen peroxide.
 4. The method ofclaim 1, wherein the aqueous well treatment fluid introduced into thewellbore further contains an aldohexose.
 5. The method of claim 1,wherein the aldohexose is selected from the group consisting of allose,altrose, glucose, mannose, gulose, idose, galactose and talose.
 6. Themethod of claim 5, wherein the aldohexose is selected from the groupconsisting of glucose, mannose and galactose.
 7. The method of claim 1,wherein the hexose oxidase is selected from the group consisting ofglucose oxidase, mannose oxidase and galactose oxidase.
 8. The method ofclaim 7, wherein the hexose oxidase is glucose oxidase.
 9. The method ofclaim 1, wherein the viscosifying agent is a polysaccharide selectedfrom the group consisting of cellulosic derivatives, galactomannan or agalactomannan derivative, xanthan, succinoglycan and scleroglucan. 10.The method of claim 9, wherein the polysaccharide is a cellulosicderivative selected from the group consisting of hydroxyalkylcelluloses, alkylcarboxyhydroxy celluloses and carboxyalkyl cellulosederivatives.
 11. The method of claim 10, wherein the cellulosicderivative is selected from the group consisting of hydroxyethylcellulose, methylhydroxyethyl cellulose, ethylhydroxyethyl cellulose,carboxymethylhydroxyethyl cellulose and methylhydroxypropyl cellulose.12. The method of claim 9, wherein the polysaccharide is selected fromthe group consisting of guar gum, hydroxypropylguar, carboxymethylguar,carboxymethylhydroxypropylguar, xanthan gum and scleroglucan.
 13. Themethod of claim 9, wherein the galactomannan or galactomannan derivativeis guar or a guar derivative.
 14. The method of claim 1, wherein themolar ratio of aldohexose:hexose oxidase in step (b) is between fromabout 1:10 to about 10:1
 15. The method of claim 1, wherein the molarratio between the aldohexose, oxygen and hexose oxidase in step (b) is1:1:1.
 16. The method of claim 1, wherein the pH of the well treatmentfluid introduced into the wellbore is between from about 5.5 to about10.5.
 17. The method of claim 1, wherein the well treatment fluidintroduced into the wellbore further comprises a crosslinking agent. 18.The method of claim 1 wherein the well treatment fluid is a fracturingfluid.
 19. The method of claim 18, where the well treatment fluid is aslickwater fracturing fluid.
 20. A method of treating a subterraneanformation penetrated by a wellbore which comprises: (a) introducing intothe wellbore an aqueous well treatment fluid having a pH between fromabout 5.5 to about 10.5, the aqueous well treatment fluid comprising aviscosifying agent or polymeric friction reducer, a crosslinking agent,an aldohexose and a hexose oxidase; (b) reacting the aldohexose withoxygen in the presence of the hexose oxidase to generate hydrogenperoxide and a carboxylated derivative of the aldohexose; (c) loweringthe pH of the well treatment fluid with the carboxylated derivative ofthe aldohexose; and (d) degrading the viscosifying agent or frictionreducer by reacting the hydrogen peroxide generated in step (b) with theviscosifying agent or friction reducer.
 21. The method of claim 20,wherein the molar ratio of aldohexose:hexose oxidase in the aqueous welltreatment fluid is between from about 1:10 to about 10:1
 22. The methodof claim 20, wherein the molar ratio of the aldohexose:oxygen:hexoseoxidase in step (b) is 1:1:1.
 23. The method of claim 20, wherein theviscosifying agent is a polysaccharide selected from the groupconsisting of guar and guar derivatives.
 24. A method of treating asubterranean formation penetrated by a wellbore which comprises: (a)introducing into the wellbore an aqueous well treatment fluid comprisinga polysaccharide and a hexose oxidase and increasing the viscosity ofthe aqueous well treatment fluid in-situ; (b) producing hydrogenperoxide in-situ by reacting an aldohexose and oxygen, in the presenceof the hexose oxidase; (c) producing a monosaccharide by reacting thehydrogen peroxide with the polysaccharide; (d) reacting themonosaccharide produced in step (c) with oxygen in the presence of thehexose oxidase to produce additional hydrogen peroxide; and (e)degrading the polysaccharide of the aqueous well treatment fluid withthe hydrogen peroxide produced in step (d).
 25. The method of claim 24,wherein the monosaccharide formed in step (c) is selected from the groupconsisting of allose, altrose, glucose, mannose, gulose, idose,galactose and talose.
 26. The method of claim 24, wherein the hexoseoxidase is selected from the group consisting of glucose oxidase,mannose oxidase and galactose oxidase.
 27. The method of claim 26,wherein the hexose oxidase is glucose oxidase.
 28. The method of claim24, wherein the pH of the aqueous well treatment fluid introduced intothe wellbore in step (a) is between from about 5.5 to about 10.5. 29.The method of claim 24, wherein the aqueous well treatment fluidintroduced into the wellbore further comprises a crosslinking agent. 30.The method of claim 24, wherein the aqueous well treatment fluidintroduced into the wellbore is a fracturing fluid.
 31. In a method ofincreasing the flow of production fluids from a subterranean formationby removing a filter cake within the subterranean formation surroundinga wellbore wherein a well treatment fluid is pumped to a specifiedlocation within the wellbore, the improvement comprising pumping intothe wellbore a well treatment fluid comprising a hexose oxidase andgenerating hydrogen peroxide in-situ in the presence of the hexoseoxidase.
 32. A method of treating a subterranean formation penetrated bya wellbore which comprises: (a) introducing into the wellbore an aqueouswell treatment fluid comprising a polysaccharide, a crosslinking agentcapable of hydrogen bonding with the polysaccharide, a hexose oxidaseand an aldohexose, the viscosity of the well treatment fluid increasingafter introduction of the aqueous well treatment fluid into thewellbore; (b) hydrolyzing the polysaccharide to form a monosaccharide;(c) activating the hexose oxidase with the aldohexose to form a reducedform of the hexose oxidase while further forming, from themonosaccharide, a lactone; (d) reacting the lactone with oxygen in thepresence of the reduced form of the hexose oxidase and water to generatehydrogen peroxide and a carboxylic acid while restoring the hexoseoxidase to its initial oxidized state; (e) degrading the polysaccharidewith the hydrogen peroxide produced in step (d); (f) reducing theefficacy of the crosslinking agent to hydrogen bonding to the polymer byreducing the pH of the fracturing fluid with the generated carboxylicacid of step (d) thereby lowering the viscosity of the well treatmentfluid.
 33. The method of claim 32, wherein the polysaccharide is guar ora guar derivative.
 34. The method of claim 32, wherein the aldohexose isselected from the group consisting of allose, altrose, glucose, mannose,gulose, idose, galactose and talose.
 35. The method of claim 34, whereinthe aldohexose is selected from the group consisting of glucose, mannoseand galactose.
 36. The method of claim 32, wherein the hexose oxidase isselected from the group consisting of glucose oxidase, mannose oxidaseand galactose oxidase.
 37. The method of claim 36, wherein the hexoseoxidase is glucose oxidase.
 38. A method of treating a subterraneanformation penetrated by a wellbore which comprises: (a) introducing intothe wellbore an aqueous viscous well treatment fluid comprising guar ora guar derivative; a crosslinking agent, a hexose oxidase and analdohexose seed, wherein guar or guar derivative hydrolyzes to amonosaccharide after being introduced into the wellbore; (b) activatingthe hexose oxidase with the aldohexose seed and producing a lactone fromthe monosaccharide; (c) reacting the lactone with oxygen in the presenceof the activated hexose oxidase to generate hydrogen peroxide; and (d)degrading the guar or guar derivative with the hydrogen peroxide.
 39. Ina method of fracturing a subterranean formation penetrated by a wellborewherein a viscous fracturing fluid comprising a polysaccharide and acrosslinking agent is introduced into the wellbore, the improvementcomprising reducing the viscosity of the fracturing fluid after it isintroduced in the wellbore with hydrogen peroxide wherein the hydrogenperoxide is produced in-situ by reaction of hydrolyzed polysaccharideand oxygen in the presence of a hexose oxidase.
 40. The method of claim39, wherein the polysaccharide is a guar or a guar derivative.
 41. Amethod of slickwater fracturing a subterranean formation comprising: (a)introducing into the wellbore an aqueous well treatment fluid void of aviscosifying polymer, wherein the well treatment fluid comprises apolymeric friction reducing agent, a hexose oxidase and an aldohexose;(b) producing hydrogen peroxide in-situ by reacting an aldohexose andoxygen, in the presence of the hexose oxidase, (c) reducing theviscosity of the well treatment fluid by reacting the hydrogen peroxidewith the polymeric friction reducing agent.